TWI438210B - A polymer compound and an organic electroluminescent device using the same - Google Patents

Description

Polymer compound and organic electroluminescent device using same

The present invention relates to a polymer compound containing an aromatic hetero ring. More specifically, the present invention relates to an aromatic heterocyclic-containing polymer compound which is applied to an organic electroluminescence device (hereinafter also referred to as "organic EL device") and has electron transport properties and pore transport properties.

An electric field illuminating (electroluminescence) element using an organic thin film, that is, an organic EL element generally has an anode, a cathode, and an organic layer provided with at least a light-emitting layer between the electrodes. In addition to the light-emitting layer, the organic layer may be provided with an electroporation injection layer (anode buffer layer), an electroporation transport layer, an electroporation prevention layer, an electron transport layer, an electron injection layer, and the like. Generally, these layers are laminated between an anode and a cathode to constitute an organic EL element.

Non-Patent Document 1 discloses a synthesis example of a non-conjugated polymer having a triazine skeleton represented by the following formula (i) which can be applied to an organic EL device and an electric field effect transistor.

(wherein R ^{1 is} each independently a hydrogen atom, a methyl group or an n-butyl group, and each of R ^{2 is} independently a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a t-butyl group, an octyl group or a methoxy group; x and y are each independently an integer of 1 or more).

Further, Patent Document 1 discloses an organic EL device formed by using a perfluorophenyl derivative as a triazine derivative for a substituent. When an organic layer of an organic EL device is produced using such a low molecular compound, a vacuum evaporation method is generally used. Therefore, it is necessary to have a vacuum device, but the thickness of the organic layer formed is liable to be uneven.

Further, Patent Document 2 discloses an organic EL device formed using a methylimine fluorescent material having a triazine ring, and Non-Patent Document 2 discloses that an organic EL device is formed using a non-conjugated polymer having a triazine skeleton. Manufacturing example.

In addition, the amphoteric compound having a substituent having a pore transporting ability in the aromatic derivative of the electron transporting property, such as the amine derivative having a heterocyclic group described in Patent Document 3, is a compound represented by the following formula (ii). Since the position of the diphenyltriazine ring group on the aromatic group is opposite to the nitrogen atom of the diphenylamino group or the nitrogen atom of the carbazolyl group, the nitrogen atom and the nitrogen atom on the heterocyclic group are The structure has a conjugated structure, so that the compound is easy to form an excimer or the like, and the polarization of the intramolecular charge is marked, and the triplet excitation level is low. Therefore, a phosphorescent organic EL device formed using such a compound, in particular, a phosphorescent organic EL device that emits short-wavelength light has a problem of durability.

Further, in Patent Documents 4 and 5, a compound represented by the following formula (iii) and the following formula (iv) is used as a charge transporting material for a phosphorescent organic EL device.

Although these compounds have a structure in which it is difficult to form an excimer, the glass transition point is from 100 ° C to 200 ° C, and there is a problem in terms of heat resistance. When the organic layer of the organic EL device is produced by using the organic layer of the organic EL device, the low molecular compound described in Patent Documents 4 and 5 is formed by a vapor deposition method, and the method for producing the organic EL device is troublesome.

Patent Document 1: JP-A-2006-173569

Patent Document 2: JP-A-2002-129155

Patent Document 3: JP-A-2003-22893

Patent Document 4: International Publication WO 03/080760 Report

Patent Document 5: JP-A-2006-188493

Non-Patent Document 1: Macromolecular Chemistry and Physics, 2004, 205, 1633-1643

Non-Patent Document 2: Molecular Crystals and Liquid Crystals, 2006, 458, 227-235

Invention disclosure

The organic EL device using the above-described low molecular compound and polymer compound still has room for improvement in driving voltage and durability. Therefore, an object of the present invention is to provide a polymer compound which can obtain an organic EL device having a low driving voltage and high durability, and an organic EL device formed using the same.

In order to solve the problem, the inventors of the present invention have found that a specific aromatic having an electron transporting portion and a pore transporting portion (hereinafter referred to as "carrier transport" for electron transport and hole transport) as an organic EL element is used. The organic EL device of the polymer compound having a heterocyclic structure has a lower driving voltage and higher durability, and has completed the present invention.

The present invention relates, for example, to the following [1] to [20]

[1] A polymer compound comprising a constituent unit derived from a monomer represented by the following formula (1),

(In the formula (1), the plural A ^{1 is} independently an aromatic group which may have a hetero atom as a ring constituting atom, a hydrogen atom, a halogen atom, an amine group, an alkyl group having 1 to 12 carbon atoms, and a carbon number. the alkoxy group having 1 to 12 carbon atoms, or an aryloxy group of 6 to 10, a plurality of at least one of A ^1, for the condensation with heteroatoms as ring constituting atoms of a condensed polycyclic aromatic group, A ² of the The bonding position of the polycyclic aromatic group is

The bonding position is meta, and the three A ² are each independently, and may have a hetero atom as a ring-constituting atom for a 6-membered ring aromatic group, and A ¹ and A ² may be directly bonded to a ring to form a hydrogen atom of the atom. Each of them may have an aromatic group, a halogen atom, an amine group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or a carbon number of 6 to a hetero atom as a ring constituting atom. The aryloxy group of 10 is substituted, and at least one of A ¹ and A ² has a substituent having a polymerizable functional group, and each of the three X atoms is independently a carbon atom or a nitrogen atom bonded to one hydrogen atom, and three At least one of X is a nitrogen atom, and two n are each independently 1 or 2).

[2] The polymer compound according to [1], wherein the monomer represented by the above formula (1) is represented by the following formula (1-i).

(In the formula (1-i), three A ^{1 's} are each independently, and may have a hetero atom as an aromatic group for a ring constituting atom, a hydrogen atom, a halogen atom, an amine group, an alkyl group having 1 to 12 carbon atoms, An alkoxy group having 1 to 12 carbon atoms or an aryloxy group having 6 to 10 carbon atoms, and at least one of the three A ¹ groups may have a hetero atom as a condensed polycyclic aromatic group for a ring-constituting atom, The bonding position of the condensed polycyclic aromatic group of A ² is

The bonding position is meta, and the three A ² are each independently, and may have a hetero atom as a ring-constituting atom for a 6-membered ring aromatic group, and A ¹ and A ² may be directly bonded to a ring to form a hydrogen atom of the atom. Each of them may have an aromatic group, a halogen atom, an amine group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or a carbon number of 6 to a hetero atom as a ring constituting atom. Substituted by an aryloxy group of 10, at least one of A ¹ and A ² is a substituent having a polymerizable functional group, and each of X X is independently a carbon atom or a nitrogen atom bonded to one hydrogen atom, and three X atoms At least one of them is a nitrogen atom).

[3] The polymer compound according to [2], wherein one of A ¹ in the above formula (1-i) has a substituent containing a polymerizable functional group, and at least one of the three A ¹ is An oxazolyl group having a substituent containing a polymerizable functional group or a halogen atom, an amine group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms The group may have an aromatic group which has a hetero atom as a ring constituting the atom.

[4] The polymer compound according to [2] or [3], wherein the monomer represented by the above formula (1) is represented by the following formulas (A1), (A13), (A14), (A15), (A31). ), (A35), (A40), (A42), (A60), (A71), (A73), (A78), (A79), (A80), (A88), (A89), (A107) or Expressed by (A108).

[5] The polymer compound according to [1], wherein the monomer represented by the above formula (1) is represented by the following formula (1-ii).

(A ^{1 in the} formula (1-ii) is an aromatic group which may have a hetero atom as a ring constituting atom, a hydrogen atom, a halogen atom, an amine group, an alkyl group having 1 to 12 carbon atoms, and 1 to 1 carbon atom; An alkoxy group of 12 or an aryloxy group having 6 to 10 carbon atoms, and each of 4 A ^{3 is} independently a condensed polycyclic aromatic group which may have a hetero atom as a ring constituting atom, and a bond of A ¹ to A ² The junction position, and the bonding position of A ³ to A ⁴ are respectively

The bonding position is meta, and A ² and 2 A ⁴ are each independently, and may have a 6-membered ring aromatic group in which a hetero atom is used as a ring constituting atom, and A ¹ to A ⁴ are directly bonded to a ring constituting atom. The hydrogen atoms may be independently used, and may have a hetero atom as an aromatic group, a halogen atom, an amine group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or a carbon atom. The aryloxy group of 6 to 10 is substituted, and at least one of A ¹ to A ⁴ has a substituent having a polymerizable functional group, and each of X X is independently a carbon atom or a nitrogen atom bonded to one hydrogen atom. At least one of the three X atoms is a nitrogen atom).

[6] The polymer compound according to [5], wherein, in the above formula (1-ii), one A ¹ is a substituent having a polymerizable functional group, and at least one of the four A ³ is An oxazolyl group having a substituent containing a polymerizable functional group or a halogen atom, an amine group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms The group may have an aromatic group which has a hetero atom as a ring constituting the atom.

[7] The polymer compound according to [5] or [6], wherein the monomer represented by the above formula (1-ii) is represented by the following formulas (A92), (A94), (A96), (A100), (A102) or (A104).

[8] The polymer compound according to any one of [1] to [7], which further comprises a constituent unit derived from a pore transporting polymerizable compound.

[9] The polymer compound according to [8], wherein the pore transporting polymerizable compound contains a carbazole structure or a triphenylamine structure.

[10] The polymer compound according to [9], wherein the pore transporting polymerizable compound contains a carbazole structure.

[11] The polymer compound according to any one of [1] to [10], which further comprises any one of a constituent unit derived from an electron transporting polymerizable compound and a constituent unit derived from a light-emitting polymerizable compound. .

[12] The polymer compound according to [11], wherein the luminescent polymerizable compound has phosphorescent luminescence.

[13] The polymer compound according to [11] or [12] wherein the luminescent polymerizable compound is a transition metal complex.

[14] The polymer compound according to [13], wherein the transition metal complex is a ruthenium complex.

[15] The polymer compound according to any one of [11] to [14] wherein the electron transporting polymerizable compound has an aromatic heterocyclic substituent or a triaryl boron substituent.

[16] The polymer compound according to any one of [1] to [15] which is used for an organic electroluminescence device.

[17] An organic electroluminescence device comprising the polymer compound according to any one of [1] to [16].

[18] An organic electroluminescence device comprising at least one of a light-emitting layer contained in the organic layer, wherein at least one of the light-emitting layers contained in the organic layer is contained in the organic electroluminescence device including one or more organic layers between the anode and the cathode. The polymer compound as described in any one of [1] to [16].

[19] An article selected from the group consisting of a display, a backlight, an electronic photo, a photographic light source, a recording light source, an exposure light source, a reading light source, a logo, a kanban, a decoration, and an optical communication system, characterized in that [18] The organic electroluminescent device described.

[20] A method of producing an organic electroluminescence device, comprising the steps of forming an organic layer containing at least one layer of the light-emitting layer according to [17] on an anode, and forming a cathode on the organic layer. step. Moreover, for the sake of simplicity, the present invention refers to the direction from the anode to the organic layer as "upper".

The polymer compound of the present invention can provide an organic EL device having a low driving voltage and high durability.

Best form for implementing the invention

The invention will be described in detail below.

<Embodiment 1>

The polymer compound (I) of the present invention (Embodiment 1) is a polymerizable compound containing a carrier transporting property represented by the above formula (1), preferably represented by the above formula (1-i) or (1-ii) The constituent unit is obtained by polymerizing a carrier-transporting polymerizable compound represented by the above formula (1), preferably represented by the above formula (1-i) or (1-ii). When such a polymer compound (I) is used, electrons, pores, and the like can be simultaneously transported, so that an organic EL device having a low driving voltage and high durability can be obtained.

In the above formula (1), A ^{1 is} independently an aromatic group which may have a hetero atom as a ring constituting atom, a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, and 1 carbon atom. An alkoxy group of up to 12 or an aryloxy group having 6 to 10 carbon atoms.

The aromatic group may have a condensed polycyclic aromatic group, a phenyl group, a pyridyl group or a pyrimidinyl group, which may have a hetero atom as a ring-constituting atom. The substituent other than the condensed polycyclic aromatic group which may have a hetero atom as a ring constituting atom is preferably a phenyl group.

The above halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Among them, a fluorine atom and a chlorine atom are preferred, and a fluorine atom is more preferred.

The above alkyl group having 1 to 12 carbon atoms is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, octyl, decyl, 2- Ethylhexyl, dodecyl and the like. Among them, an alkyl group having 2 to 8 carbon atoms is preferred, and an alkyl group having 3 to 6 carbon atoms is more preferred.

The above alkoxy group having 1 to 12 carbon atoms is, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, t-butoxy, hexyloxy, 2 Ethylhexyloxy, nonyloxy, dodecyloxy and the like. Among them, an alkoxy group having 2 to 8 carbon atoms is preferred, and an alkoxy group having 3 to 6 carbon atoms is more preferred.

The above aryloxy group having 6 to 10 carbon atoms is, for example, a phenoxy group, a benzyloxy group, a phenethyloxy group, a phenylpropoxy group, a phenylbutoxy group or the like. Among them, a phenoxy group, a benzyloxy group and a phenethyloxy group are preferred, and a phenoxy group is more preferred.

In the above formula (1), at least one of A ¹ is a condensed polycyclic aromatic group having a hetero atom as a ring-constituting atom.

The above condensed polycyclic aromatic group such as naphthyl, anthracenyl, phenanthryl, anthryl, butyl, pentyl, fluorenyl, triphosphoryl, anthracenyl, fluorenyl, oxazolyl, benzene And oxazolyl, benzothiazolyl, benzothienyl, dibenzofuranyl, dibenzothiophenyl, azaindole, quinolyl, pyridodecyl, benzothiadiazolyl, etc. Preferred among them are a carbazolyl group, a fluorenyl group, an azaindole group and a pyridoindole group, more preferably an oxazolyl group and a fluorenyl group, and particularly preferably an oxazolyl group.

In the above formula (1), each of the three A ² groups may be independently an aromatic group which may have a hetero atom as a ring constituting atom.

The above aromatic group is, for example, a phenyl group, a pyridyl group, a pyrimidinyl group or the like. Among them, a phenyl group is preferred.

In the above formula (1), the direct bonding ring of A ¹ and A ² may constitute a hydrogen atom of an atom, and may have a hetero atom as an aromatic group, a halogen atom, a cyano group or a carbon atom. An alkyl group of 1 to 12, an alkoxy group having 1 to 12 carbon atoms or an aryloxy group having 6 to 10 carbon atoms is substituted.

The above aromatic group is, for example, a phenyl group, a pyridyl group or a pyrimidinyl group. Among them, a phenyl group and a pyridyl group are preferred, and a phenyl group is more preferred.

The above halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Among them, a fluorine atom and a chlorine atom are preferred, and a fluorine atom is more preferred.

The above alkyl group having 1 to 12 carbon atoms is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, octyl, decyl, 2- Ethylhexyl, dodecyl and the like. Among them, an alkyl group having 2 to 8 carbon atoms is preferred, and an alkyl group having 3 to 6 carbon atoms is more preferred.

The above alkoxy group having 1 to 12 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, t-butoxy, hexyloxy Base, 2-ethylhexyloxy, decyloxy, dodecyloxy and the like. Among them, an alkoxy group having 2 to 8 carbon atoms is preferred, and an alkoxy group having 3 to 6 carbon atoms is more preferred.

The above aryloxy group having 6 to 10 carbon atoms is, for example, a phenoxy group, a benzyloxy group, a phenethyloxy group, a phenylpropoxy group, a phenylbutoxy group or the like. Among them, a phenoxy group, a benzyloxy group and a phenethyloxy group are preferred, and a phenoxy group is more preferred.

In the above formula (1), at least one of A ¹ is a condensed polycyclic aromatic group which may have a hetero atom as a ring-constituting atom, and represents A ¹ to A of the condensed polycyclic aromatic group and the aromatic group. The bonding position of ² is, right (ie, the bonding position of the pyridine ring, the pyrimidine ring or the triazine ring) is a meta position. For example, when A ² is a 6-membered ring aromatic group which is composed only of a carbon atom as a ring-constituting atom, the bonding position is as follows ( Expressed by i) or (ii). The monomer represented by the above formula (1) is preferred because it has excellent resistance to electrical oxidation and is not easily formed into an excimer.

In the above formula (1), at least one of A ¹ and A ² is a substituent having a polymerizable functional group. Among them, in order to obtain an organic EL device having higher luminous efficiency, it is preferred that at least one A ¹ is a substituent having a polymerizable functional group. The substituent having a polymerizable functional group may also contain a polymerizable functional group.

The polymerizable functional group may be any of a functional group of a radical polymerizable property, a cationic polymerizable property, an anionic polymerizable property, an addition polymerizable property, and a condensation polymerizable property. Among them, the polymerizable property is preferably a radical polymerizable functional group.

Specific examples of the above polymerizable functional group include, for example, an allyl group; an alkenyl group; an acrylate group; a methacrylate group; a methacrylic acid ethyl urethane group or the like. ) an acrylate group; a vinyl amide group; and derivatives thereof.

Specifically, the substituent having the above polymerizable functional group is preferably a substituent represented by the following general formula (7).

In the above formula (7), R ⁷⁰¹ is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.

The above alkyl group having 1 to 12 carbon atoms is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, octyl, decyl, 2- Ethylhexyl, dodecyl and the like. Among them, it has excellent carrier transport energy, and R ^{701 is} preferably a hydrogen atom.

X ⁷ is a single bond or a group represented by the following formulae (X71) to (X74).

In the formula, R ^X71 is a single bond or an alkylene group having 1 to 12 carbon atoms, and R ^X72 is a single bond, an alkylene group having 1 to 12 carbon atoms or a phenyl group. Further, in the above formula (1), R ^{X71 is} bonded to A ¹ and R ^{X72 is} bonded to the vinyl group. Such an X ⁷ can obtain an organic EL element having a lower driving voltage and higher durability.

The above alkyl group having 1 to 12 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, and Hexyl, octyl, decyl, 2-ethylhexyl, and dodecyl. Among them, an alkylene group having 1 to 6 carbon atoms is preferred, and an alkylene group having 1 to 3 carbon atoms is more preferred.

Wherein X ^{7 is} preferably a single bond or an alkylene group having 1 to 7 carbon atoms, more preferably a single bond.

In the above formula (1), one A ¹ is a substituent having a polymerizable functional group represented by the above formula (7), and at least one of the plurality of A ¹ may have a halogen atom or an amine group. The alkyl group having 1 to 12 carbon atoms or the aryloxy group having 6 to 10 carbon atoms may preferably have a hetero atom as the carbazolyl group of the substituent of the ring-constituting atom or the substituent of the polymerizable functional group.

Specific examples of the substituent such as a halogen atom and an alkyl group may be the same as described above.

In order to impart excellent solubility and carrier transporting ability to the monomer represented by the above formula (1), A ¹ in the above formula (1) is particularly preferable, and one A ¹ is a polymerizable property represented by the above formula (7). a functional group-substituted carbazolyl group, and bonding A ² representing A ¹ of the carbazolyl group to the above formula (i) or (ii), or 1 A ¹ being represented by the above formula (7) The polymerizable functional group, and at least one of A ¹ in the other A ^{1 is} in the form of a carbazolyl group.

In the above formula (1), three X atoms are carbon atoms or nitrogen atoms bonded to one hydrogen atom, and at least one of the three X atoms is a nitrogen atom. That is, the monomer represented by the above formula (1) has any one of a pyridine ring skeleton, a pyrimidine ring skeleton, and a triazine ring skeleton.

In order to make the monomer represented by the above formula (1) have excellent resistance to electrochemical oxidation, and it is not easy to form an excimer, two n's are all 1 (that is, represented by the above formula (1-i)) And two instances in which n is 2 (that is, represented by the above formula (1-ii)) are preferred.

In the above formula (1-ii), each of A ^{3 is} independently a condensed polycyclic aromatic group which may have a hetero atom as a ring-constituting atom, and such a condensed polycyclic aromatic group is the same as A ¹ in the above formula (1).

A ^{4 in the} above formula (1-ii) is independently a 6-membered ring aromatic group which may have a hetero atom as a ring-constituting atom, and the aromatic group is the same as A ² in the above formula (1).

In the above formula (1-ii), the hydrogen atoms directly bonded to the ring-constituting atoms in A ¹ to A ⁴ may be independently used, and may have a hetero atom as an aromatic group, a halogen atom, an amine group or a carbon for forming a ring. The alkyl group having 1 to 12 atoms, the alkoxy group having 1 to 12 carbon atoms or the aryloxy group having 6 to 10 carbon atoms is substituted with A ¹ and A ² in the above formula (1).

At least one of A ¹ to A ⁴ in the above formula (1-ii) is a substituent having a polymerizable functional group. Among them, in order to obtain an organic EL device having higher luminous efficiency, at least one of A ¹ is a substituent having a polymerizable functional group. Further, the substituent having a polymerizable functional group also contains a polymerizable functional group.

Such a polymerizable functional group and a substituent having the same are the same as described above.

Specific examples of the monomer represented by the above formula (1-i), for example, a monomer represented by the following formula (A1) to (A90), (A107) or (A108), represented by the above formula (i-ii) Specific examples of the monomer include monomers represented by the following formulas (A91) to (A106), but the present invention is not limited thereto.

Among them, the above formulas (A1), (A13), (A14), (A15), (A31), (A35), (A40), (A42), (A60), (A71), (A73), (A78), (A79), (A80), (A88), (A89), (A92), (A94), (A96), (A100), (A102), (A104), (A107), and (A108) More preferably, the compound represented by any one of the formulae (A13), (A15), (A31), (A40), (A60), (A71), (A78), (A80), (A88) and A compound represented by any one of (A107).

The carrier-transporting polymerizable compound may be used singly or in combination of two or more kinds.

Such a carrier-transporting polymerizable compound can be obtained by, for example, using a Lewis acid to cyclize the benzonitrile with 3-bromo-5-iodophenylhydrazine chloride, and then sequentially reacting the vinylphenylboronic acid and the oxime with a bell. Oxazole can be coupled to manufacture.

Further, when the polymer compound (I) is produced, another polymerizable compound may be used. The other polymerizable compound is, for example, a compound having no carrier transport property such as alkyl (meth)acrylate such as methyl acrylate or methyl methacrylate, or styrene or a derivative thereof, but is not limited thereto. In the polymer compound (I), the content of the structural unit derived from the other polymerizable compound is preferably from 0 to 50 mol% in 100 mol% of all structural units.

When the polymerizable compound is used in the production of the polymer compound (I), any of radical polymerization, cationic polymerization, anionic polymerization, and addition polymerization may be carried out, but radical polymerization is preferred.

The weight average molecular weight of the polymer compound (I) is usually from 1,000 to 2,000,000, preferably from 5,000 to 500,000. When the weight average molecular weight is in this range, the polymer compound (I) is soluble in an organic solvent, and a uniform film is preferred. The weight average molecular weight is a value measured by a gel permeation chromatography (GPC) method using tetrahydrofuran as a solvent at 40 °C.

The solubility of the polymer compound (I) in an organic solvent such as toluene or chloroform is preferably such that 1 part by mass of the polymer compound (I) is dissolved in the organic solvent in an amount of 1 to 200 parts by mass, more preferably 10 to 50 parts by mass. The amount of mass. When the solubility is in this range, it is preferred to form a film by a coating method.

<Embodiment 2>

The polymer compound (II) of the present invention (the second embodiment) is a unit of a polymerizable compound derived from the carrier transporting property represented by the above formula (1), and further contains a unit derived from a polymerizable compound having a pore transporting property. a carrier-transporting polymerizable compound represented by the above formula (1) and The pore-transporting polymerizable compound is obtained by polymerization.

The carrier-transporting polymerizable compound represented by the above formula (1) is the same as the preferred range and the reason for the carrier-transporting polymerizable compound used in the first embodiment.

The pore transporting polymerizable compound preferably contains a substituent having a polymerizable functional group, a carbazole group-containing structure or a triphenylamine structure, and more preferably a carbazole structure.

Such a polymerizable compound containing a carbazole structure or a triphenylamine structure, for example, N,N'-diphenyl-N,N'-(3-methylphenyl) having a substituent having a polymerizable functional group -1,1'-biphenyl-4,4'-diamine (TPD), N,N,N',N'-tetrakis(3-methylphenyl)-1,1'-(3,3 '-Dimethyl)biphenyl-4,4'-diamine (HMTPD), 4,4',4"-tris(3-methylphenylphenylamino)triphenylamine (m-MTDATA) , 9-vinylcarbazole, 9-ethylcarbazole, 4,4'-biscarbazolylbiphenyl (CBP), 4,4'-biscarbazolyl, 2,2'-dimethyl linkage Benzene (CDBP), etc. Among them, preferred are 9-vinylcarbazole, 9-ethylcarbazole, CBP and CDBP, more preferably 9-ethylcarbazole and CDBP.

The above-mentioned pore-transporting polymerizable compounds may be used alone or in combination of two or more.

Further, the polymerizable compound having a pore transporting property represented by the following general formulas (5) and (6) is suitable for use in the present invention because it has excellent carrier transport energy and photophysical properties.

In the above formula (5), at least one of R ⁵⁰¹ to R ⁵²⁴ is a substituent having a polymerizable functional group, and R ⁵⁰¹ to R ^{524 which} are not a substituent having a polymerizable functional group are each independently capable of being a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkyl group substituted with an alkyl group having 1 to 10 carbon atoms, and 1 to 10 carbon atoms. An atom or substituent selected from the group consisting of an alkoxy group, a carbazolyl group, and a decyl group.

Specific examples of the above atom or substituent are, for example, the above atom or a substituent. The above carbazolyl group may have a substituent such as a methyl group, an ethyl group, a t-butyl group or a methoxy group.

In R ⁵⁰¹ to R ⁵⁰⁵ , R ⁵⁰⁶ to R ⁵¹⁰ , R ⁵¹¹ to R ⁵¹⁵ , R ⁵¹⁶ to R ⁵²⁰ and R ⁵²¹ to R ⁵²³ , two groups adjacent to each other through two carbon atoms constituting the ring may be mutually Bonding to form a condensed ring.

In the above formula (6), at least one of R ⁶⁰¹ to R ⁶³³ is a substituent having a polymerizable functional group, and R ⁶⁰¹ to R ^{633 which} are not a substituent having a polymerizable functional group are each independently capable of being a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkyl group substituted with an alkyl group having 1 to 10 carbon atoms, and 1 to 10 carbon atoms. An atom or a substituent selected from the group consisting of an alkoxy group and a decyl group.

Specific examples of the above atom or substituent are, for example, the above atom or a substituent.

R ⁶⁰¹ to R ⁶⁰⁵ , R ⁶⁰⁶ to R ⁶¹⁰ , R ⁶¹¹ to R ⁶¹⁵ , R ⁶¹⁶ to R ⁶²⁰ , R ⁶²¹ to R ⁶²⁵ , and R ⁶²⁶ to R ⁶³⁰ are adjacent to each other by two carbon atoms constituting the ring. The two groups may also be bonded to each other to form a condensed ring.

Preferably, in the polymerizable compound represented by the above formula (5), R ⁵⁰¹ to R ⁵⁰⁵ , R ⁵⁰⁶ to R ⁵¹⁰ , R ⁵¹¹ to R ⁵¹⁵ , and R ⁵¹⁶ to R ⁵²⁰ are each at least one of hydrogen atoms. The above atom or substituent. R ⁵⁰¹ to R ⁵²⁴ which are not a polymerizable functional group or the above atom or substituent at this time are a hydrogen atom. Further, in the polymerizable compound represented by the above formula (6), R ⁶⁰¹ to R ⁶⁰⁵ , R ⁶⁰⁶ to R ⁶¹⁰ , R ⁶¹¹ to R ⁶¹⁵ , R ⁶¹⁶ to R ⁶²⁰ , R ⁶²¹ to R ⁶²⁵ , and R ⁶²⁶ to Each of R ⁶³⁰ is at least one of the above atoms or substituents other than a hydrogen atom. R ⁶⁰¹ to R ⁶³³ which are not a polymerizable functional group or the above atom or substituent at this time are a hydrogen atom.

The substituent having a polymerizable functional group is preferably a substituent represented by the above general formula (7). R ⁷⁰¹ is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. The preferred range of R ⁷⁰¹ and the reason thereof are the electron transporting polymerizable compounds described in the first embodiment. X ⁷ is a single bond or a group represented by the above formulae (X71) to (X74). The preferred range and reason for X ^{7 are} the electron transporting polymerizable compounds described in the first embodiment.

The above-mentioned pore-transporting polymerizable compound is more specifically a compound represented by the following formulas (8-1) to (8-11).

The above-mentioned pore-transporting polymerizable compounds may be used alone or in combination of two or more.

The compound represented by the above formula (5) may be, for example, a palladium catalyst substitution reaction of an n-phenylenediamine derivative with an aryl halide or a palladium catalyst of a diarylamine and an m-dibromobenzene derivative. The reaction comes. Specific methods for the substitution reaction are described in Tetrahedron Letters, 1998, Vol. 39, p. 2367.

Further, the compound represented by the above formula (6) may be, for example, a palladium catalyst substitution reaction of 1,3,5-triaminobenzene with a halogenated aryl ester, or a diarylamine and 1,3,5-trihalogenated benzene. The palladium catalyst is substituted for the reaction. Specific methods for the substitution reaction are described, for example, in Tetrahedron Letters, 1998, Vol. 39, p. 2367.

The above-described formula (1), at least three of A ¹ A ¹ is a hetero atom may have a ring-constituting atoms of a condensed polycyclic aromatic group (preferably carbazolyl), thus transporting the polymerizable mesoporous Since the compound has a carbazole structure, it is preferable to reduce the difference in polymerization reactivity between the polymerizable compound having a carrier transport property and the polymerizable compound having a pore transporting property.

Further, another polymerizable compound which can be additionally used in the production of the polymer compound (II) is the same as in the first embodiment.

When the polymerizable compound is used in the production of the polymer compound (II), any of radical polymerization, cationic polymerization, anionic polymerization, and addition polymerization may be carried out, but radical polymerization is preferred.

The weight average molecular weight of the polymer compound (II) is the same as in the first embodiment. Further, the solubility of the polymer compound (II) in an organic solvent is the same as in the first embodiment.

In the polymer compound (II), the number of constituent units of the polymerizable compound derived from the pore transporting property is m, and when the number of constituent units of the polymerizable compound derived from the carrier of the formula (1) is n. (m and n are integers of 1 or more), and the ratio of the constituent unit numbers of the polymerizable compound derived from the pore transporting property, that is, the value of m/(m+n) is preferably 0.1 to 0.9, more preferably, based on the total number of constituent units. When the value is from 0.2 to 0.9, particularly preferably from 0.4 to 0.9, and m/(m + n) is in this range, an organic EL device having high carrier mobility and durability can be obtained. Further, the ratio of each constituent unit in the polymer compound can be determined by ICP elemental analysis and ¹³ C-NMR measurement.

In addition, when the ratio of the carrier-transporting polymerizable compound and the pore-transporting polymerizable compound is appropriately adjusted to the above range, the polymer compound (II) having a desired structure can be obtained.

Further, the polymer compound (II) may be any of a random copolymer, a block copolymer and an interactive copolymer.

<Embodiment 3>

The polymer compound (III) of the present invention (Example 3) is a constituent unit of a polymerizable compound derived from the carrier transporting property represented by the above formula (1), and a constituent unit of a polymerizable compound derived from pore transportability. Further, the constituent unit derived from the luminescent polymerizable compound is obtained by polymerizing a carrier-transporting polymerizable compound represented by the above formula (1), a polymerizable compound having pore transportability, and a polymerizable compound having luminescence.

The carrier-transporting polymerizable compound represented by the above formula (1) and the polymerizable compound having pore transportability are the same as those of the carrier-transporting polymerizable compound used in the second embodiment.

The luminescent polymerizable compound preferably has a phosphorescent property, more preferably a transition metal complex having a substituent containing a polymerizable functional group, and particularly preferably a ruthenium complex having a substituent having a polymerizable functional group. Things.

Such a ruthenium complex is preferably a complex represented by the following general formulas (2) to (4). These polymerizable compounds have a vinyl group having a polymerizable functional group.

In the above formula (2), R ²⁰¹ to R ²¹⁵ are each independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a carbon atom number. An atom or a substituent selected from the group consisting of an alkyl group-substituted amino group of 1 to 10, an alkoxy group having 1 to 10 carbon atoms, and a decyl group.

The above halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

The above alkyl group having 1 to 10 carbon atoms is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, an octyl group or a decyl group.

The above aryl group having 6 to 10 carbon atoms is, for example, a phenyl group, a tolyl group, a xylyl group, Base, naphthyl and the like.

The above-mentioned amine group which may be substituted with an alkyl group having 1 to 10 carbon atoms is, for example, an amine group, a dimethylamino group, a diethylamino group, a dibutylamino group or the like.

The above alkoxy group having 1 to 10 carbon atoms is, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, t-butoxy, hexyloxy, 2 Ethylhexyloxy, decyloxy and the like.

The above alkylene group is, for example, trimethyldecylalkyl, triethyldecylalkyl, t-butyldimethylmethylalkyl, trimethoxydecylalkyl or the like.

In order to obtain excellent phosphorescence, R ²⁰¹ to R ^{215 are} preferably a hydrogen atom, a fluorine atom, a cyano group, a methyl group, a t-butyl group, a dimethylamino group, a butoxy group or a 2-ethylhexyloxy group. More preferably, R ²⁰² is a t-butyl group, except that R ²⁰¹ to R ²¹⁵ of R ²⁰² are a hydrogen atom.

In R ²⁰¹ to R ²⁰⁴ , R ²⁰⁵ to R ²⁰⁸ , R ²⁰⁹ to R ²¹¹ , and R ²¹² to R ²¹⁵ , two groups adjacent to each other via two carbon atoms constituting the ring may be bonded to each other to form a condensed ring.

R ²¹⁶ is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. The above alkyl group having 1 to 12 carbon atoms is as the above alkyl group. In order to obtain excellent carrier transportability, R ^{216 is} preferably a hydrogen atom.

X ² is a single bond or a group represented by the following formulas (X21) to (X24).

In the formula, R ^X21 is a single bond or an alkylene group having 1 to 12 carbon atoms, and R ^X22 is a single bond, an alkylene group having 1 to 12 carbon atoms or a phenyl group. Further, in the above formula (2), R ^{X21 is} preferably bonded to a benzene ring, and R ^{X22 is} bonded to a vinyl group. Since X ² does not contain a hetero atom, an organic EL element having higher luminous efficiency can be obtained.

In the above formula (3), R ³⁰¹ to R ³⁰⁸ are each independently an atom or a substituent of the same R ²⁰¹ .

R ³⁰⁹ to R ³¹⁰ are each independently an atom or a substituent of R ²⁰¹ (except for a halogen atom).

In order to obtain excellent phosphorescence, R ³⁰¹ to R ^{310 are} preferably each independently a hydrogen atom, a fluorine atom, a cyano group, a methyl group, a t-butyl group, a dimethylamino group, a butoxy group, or a 2- Ethylhexyloxy, more preferably R ³⁰² is t-butyl, except that R ³⁰¹ to R ³¹⁰ of R ³⁰² are a hydrogen atom.

In R ³⁰¹ to R ³⁰⁴ and R ³⁰⁵ to R ³⁰⁸ , two adjacent groups may be bonded to each other to form a condensed ring via two carbon atoms constituting the ring.

R ³¹¹ is an atom or a substituent of the same R ²¹⁶ , and the preferred range and the reason are also the same as R ²¹⁶ .

X ³ is a single bond or a group represented by the following formulas (X31) to (X34).

In the formula, R ^X31 is a single bond or an alkylene group having 1 to 12 carbon atoms, and R ^X32 is a single bond, an alkylene group having 1 to 12 carbon atoms or a phenyl group. The preferred range and reason for X ^{3 is} the same as X ² .

In the above formula (4), R ⁴⁰¹ to R ⁴¹¹ are each independently the same as R ²⁰¹ atom or a substituent. In order to obtain excellent phosphorescence, R ⁴⁰¹ to R ^{411 are} preferably each independently a hydrogen atom, a fluorine atom, a cyano group, a methyl group, a t-butyl group, a dimethylamino group, a butoxy group, or a 2- Ethylhexyloxy, more preferably R ⁴⁰² is a t-butyl group, except that R ⁴⁰¹ to R ⁴¹¹ of R ⁴⁰² are a hydrogen atom.

In R ⁴⁰¹ to R ⁴⁰⁴ , R ⁴⁰⁵ to R ⁴⁰⁸ , and R ⁴⁰⁹ to R ⁴¹¹ , two adjacent groups may be bonded to each other to form a condensed ring via two carbon atoms constituting the ring.

R ⁴¹² is an atom or a substituent of the same R ²¹⁶ , and the preferred range and the reason are also the same as R ²¹⁶ .

X ⁴ is a single bond or a group represented by the following formulas (X41) to (X44).

^Wherein R ^X41 is a single bond or an alkylene group having 1 to 12 carbon atoms, and R ^X42 is a single bond, an alkylene group having 1 to 12 carbon atoms or a phenyl group. The preferred range and reason for X ^{4 is} the same as X ² .

The above-mentioned phosphorescent polymerizable compounds may be used alone or in combination of two or more.

Such a phosphorescent polymerizable compound can be, for example, reacted with phenyl chloride and a phenylpyridine derivative to form a dinuclear complex of silver (Ir), and a ligand having a polymerizable functional group (the above formula ( 2) The reaction is carried out by reacting the ligand located on the right side of Ir in (4).

Further, another polymerizable compound which can be used separately when the polymer compound (III) is produced is the same as in the first embodiment.

When the polymerizable compound is used in the production of the polymer compound (III), any of radical polymerization, cationic polymerization, anionic polymerization, and addition polymerization may be carried out, and radical polymerization is preferred.

The weight average molecular weight of the polymer compound (III) is the same as in the first embodiment. The solubility of the polymer compound (III) in an organic solvent is the same as in the first embodiment.

In the polymer compound (III), the structural unit number of the polymerizable compound derived from the phosphorescent property is x, and the structural unit of the polymerizable compound derived from the carrier transporting property and the pore transporting property represented by the above formula (1) When the number is y (x, y is an integer of 1 or more), the structural unit ratio of the phosphorescent polymerizable compound relative to the total number of structural units, that is, the value of x/(x+y) is preferably 0.001. A range of up to 0.5 is more preferably in the range of 0.001 to 0.2. When the value of x/(x+y) is in this range, an organic EL element having a large carrier mobility, a small concentration extinction effect, and a high luminous efficiency can be obtained.

In the polymer compound (III), the number of structural units of the polymerizable compound derived from the pore transportability is m, and when the number of structural units of the polymerizable compound derived from the carrier transportability is n (m, n is 1 or more) The integer) and the above y are in accordance with the relationship of y=m+n. The structural unit number ratio m/y of the polymerizable compound derived from the pore transporting property and the optimum structural value ratio n/y of the polymerizable compound derived from the carrier transportability with respect to the number of structural units derived from the charge transporting compound. It is determined by the charge transport energy, concentration, etc. of each structural unit. When the light-emitting layer of the organic EL device is formed of the polymer compound (III), the values of m/y and n/y are preferably from 0.05 to 0.95, more preferably from 0.20 to 0.80. Also, m/y+n/y=1. In the above polymer compound, the ratio of each structural unit can be determined by ICP elemental analysis and ¹³ C-NMR measurement.

Further, the carrier-transporting polymerizable compound and the pores are transported When the ratio of the polymerizable compound and the above-mentioned phosphorescent polymerizable compound is appropriately adjusted to the above range, the polymer compound (III) having a desired structure can be obtained.

Further, the polymer compound (III) may be any of a random copolymer, a block copolymer and an interactive copolymer.

<Embodiment 4>

The polymer compound (IV) of the present invention (Example 4) contains, in addition to the constituent unit of the carrier-transporting polymerizable compound represented by the above formula (1) and the constituent unit of the polymerizable compound derived from pore transportability, The constituent unit of the electron transporting polymerizable compound is obtained by polymerizing a carrier transporting polymerizable compound represented by the above formula (1), a pore transporting polymerizable compound, and an electron transporting polymerizable compound.

The carrier-transporting polymerizable compound represented by the above formula (1) and the polymerizable compound having pore transportability are the same as those of the carrier-transporting polymerizable compound used in the second embodiment.

The electron transporting polymerizable compound is preferably an aromatic heterocyclic structure or a triaryl boron structure containing a substituent having a polymerizable functional group, and more preferably an aromatic ring structure.

Further, another polymerizable compound which can be used separately when the polymer compound (IV) is produced is the same as in the first embodiment.

When the polymerizable compound is used in the production of the polymer compound (IV), any of radical polymerization, cationic polymerization, anionic polymerization, and addition polymerization may be carried out, but radical polymerization is preferred.

The weight average molecular weight of the polymer compound (IV) is the same as in the first embodiment. The dissolution of the polymer compound (IV) in an organic solvent is the same as in the first embodiment.

In the polymer compound (IV), the number of units of the polymerizable compound derived from electron transport property is x', the number of constituent units of the polymerizable compound derived from pore transportability is y', and the formula (1) When the number of constituent units of the carrier-transporting polymerizable compound represented by z is z'(x',y', and z' are integers of 1 or more), the polymerizable compound derived from electron transportability is formed for all the unit numbers. The ratio of the constituent unit ratio, that is, x'/(x'+y'+z') is preferably from 0.1 to 0.9, more preferably from 0.1 to 0.5, particularly preferably from 0.1 to 0.3. When the value of x'/(x'+y'+z') is in this range, an organic EL element having a high carrier mobility and high durability can be obtained. The ratio of each constituent unit of the above polymer compound can be determined by ICP elemental analysis and ¹³ C-NMR measurement.

In addition, when the ratio of the carrier-transporting polymerizable compound, the pore-transporting polymerizable compound, and the electron-transporting polymerizable compound is appropriately adjusted within the above range, polymerization can be performed to obtain a desired structure. Molecular compound (IV).

Further, the polymer compound (IV) may be any of a random copolymer, a block copolymer and an interactive copolymer.

<Embodiment 5>

The polymer compound (V) of the present invention (Example 5) is a constituent unit containing a carrier-transporting polymerizable compound represented by the above formula (1), and a constituent unit of a polymerizable compound derived from pore transportability. The constituent unit of the electron-transporting polymerizable compound and the constituent unit of the polymerizable compound derived from the luminescent property, the carrier-transporting polymerizable compound represented by the above formula (1), the polymerizable compound having pore transportability, and electron transport The polymerizable compound is obtained by polymerizing a luminescent polymerizable compound.

The carrier-transporting polymerizable compound represented by the above formula (1), the pore-transporting polymerizable compound, the electron-transporting polymerizable compound, and the luminescent polymerizable compound are the same as those used in the first to fourth embodiments. The compounds, preferred ranges and reasons are the same.

Further, another polymerizable compound which can be additionally used in the production of the polymer compound (V) is the same as in the first embodiment.

When the polymerizable compound is used in the production of the polymer compound (V), any of radical polymerization, cationic polymerization, anionic polymerization, and addition polymerization may be carried out, but radical polymerization is preferred.

The weight average molecular weight of the polymer compound (V) is the same as in the first embodiment. The solubility of the polymer compound (V) in an organic solvent is the same as in the first embodiment.

In the polymer compound (V), the number of constituent units of the polymerizable compound derived from electron transport property is p, and the number of constituent units of the polymerizable compound derived from luminescent properties is q, and the polymerizable compound derived from pore transportability The number of constituent units is r, and the number of constituent units of the polymerizable compound derived from the carrier transporting property represented by the above formula (1) is s (p to s are each an integer of 1 or more); The structural unit ratio of the electron transporting polymerizable compound, that is, the value of p/(p+q+r+s) is preferably from 0.1 to 0.9, more preferably from 0.1 to 0.5, particularly preferably from 0.1 to 0.3. In addition, the value of the constituent unit ratio of the luminescent polymerizable compound, that is, q/(p+q+r+s), is preferably 0.001 to 0.5, more preferably 0.001 to 0.2. When the number of constituent units of the polymerizable compound having electron transporting property and luminescent property is within this range, the organic EL device having a high carrier mobility and high durability can be obtained. The ratio of each constituent unit of the above polymer compound can be determined by ICP elemental analysis and ¹³ C-NMR measurement.

In addition, when the ratio of the carrier-transporting polymerizable compound, the pore-transporting polymerizable compound, the electron-transporting polymerizable compound, and the luminescent polymerizable compound is appropriately adjusted to the above range, the polymerization can be carried out. A polymer compound (V) having a desired structure is obtained.

Further, the polymer compound (V) may be any of a random copolymer, a block copolymer and an interactive copolymer.

<Embodiment 6>

In the organic EL device of the present invention (the embodiment 6), a unit containing a specific polymer compound (I), a luminescent compound to be described later, and a polymerizable compound having pore transport properties to be described later is provided between the anode and the cathode. A light-emitting layer of a polymer compound (I'). In this case, the light-emitting layer is preferably contained in an amount of 0.1 to 50 parts by mass, more preferably 0.5 to 30 parts by mass, based on 100 parts by mass of the polymer compound (I), and a polymer compound (I'). ) 10 to 200 parts by mass, more preferably 50 to 150 parts by mass. When the carrier-transporting polymer compound (I), the luminescent compound, and the pore-transporting polymer compound (I') form a light-emitting layer, even if another organic material layer is not provided, high light emission can be produced. An efficient organic EL element.

The luminescent compound is preferably a phosphorescent compound, more preferably a ruthenium complex.

Specific examples of the above-mentioned oxime complexes are the following complexes (E-1) to (E-39).

Among them, preferred are compounds represented by any one of E-1, E-2, E-6, E-33, E-34, E-38 and E-39, more preferably E-33 and E-38. Any compound represented by the formula.

These luminescent compounds may be used alone or in combination of two or more.

The polymer compound (I') can be obtained by polymerizing a pore-transporting polymerizable compound. The pore transporting polymerizable compound is the same as the preferred range and the reason for the pore transporting polymerizable compound used in the third embodiment.

When the polymerizable compound is used in the production of the polymer compound (I'), any of radical polymerization, cationic polymerization, anionic polymerization, and addition polymerization may be carried out, but radical polymerization is preferred.

The weight average molecular weight of the polymer compound (I') is generally 1,000 to 2,000,000, preferably 5,000 to 500,000. When the weight average molecular weight is in this range, the polymer compound (I') is soluble in an organic solvent, and a uniform film is preferred. The weight average molecular weight is a value measured by a gel permeation chromatography (GPC) method using tetrahydrofuran as a solvent at 40 °C. Further, the solubility of the polymer compound (I') in an organic solvent is the same as in the first embodiment.

When an organic EL device comprising a light-emitting layer containing a polymer compound (I), a light-emitting compound, and a polymer compound (I') is provided between the anode and the cathode, the light-emitting layer is generally formed by the following method. It is placed on the anode on the substrate. First, a solution of the dissolved polymer compound (I), the luminescent compound, and the polymer compound (I') is prepared. The solvent for preparing the above solution is not particularly limited. For example, a chlorine solvent such as chloroform, dichloromethane or dichloroethane, an ether solvent such as tetrahydrofuran or anisole, or an aromatic hydrocarbon solvent such as toluene or xylene may be used. A ketone solvent such as acetone or methyl ethyl ketone, an ester solvent such as ethyl acetate, butyl acetate, ethyl cellosolve or acetate. Secondly, using spin coating method, casting method, micro gravure method, gravure method, bar coating method, roll coating method, wire rod coating method, dip coating method, spray coating method, screen printing method, flexographic printing A wet film formation method such as a printing method, a lithography method, or an inkjet printing method, or the like, is formed into a film on a substrate. Further, depending on the compound to be used, the film formation conditions, and the like, for example, when the spin coating method or the dip coating method is used, the solution preferably contains the luminescent compound 0.5 based on 100 parts by mass of the polymer compound (I). To 30 parts by mass, the polymer compound (I') is used in an amount of 10 to 200 parts by mass, and the solvent is used in an amount of 1,000 to 20,000 parts by mass.

After the cathode is provided on the light-emitting layer formed as described above, the organic EL device of the sixth embodiment can be obtained.

Moreover, it is preferable that the substrate used in the sixth embodiment is an insulating substrate having a transparent light-emitting wavelength with respect to the light-emitting material, and in particular, in addition to glass, PET (polyethylene terephthalate) may be used. Transparent plastic such as polycarbonate.

Further, the anode material used in the sixth embodiment is preferably a known transparent conductive material such as a conductive polymer such as ITO (indium tin oxide), tin oxide, zinc oxide, polythiophene, polypyrrole or polyaniline. The surface resistance of the electrode formed of the transparent conductive material is preferably from 1 to 50 Ω/□ (ohm/rectangular). The thickness of the anode is preferably from 50 to 300 nm.

Further, the cathode material used in the sixth embodiment is preferably an alkali metal such as Li, Na, K or Cs; an alkaline earth metal such as Mg, Ca or Ba; Al; a MgAg alloy; Al such as AlLi or AlCa, and an alkali metal or alkaline earth. Known cathode materials such as metal-like alloys. The thickness of the cathode is preferably from 10 nm to 1 μm, more preferably from 50 to 500 nm. When a metal having a higher activity such as an alkali metal or an alkaline earth metal is used, the thickness of the cathode is preferably from 0.1 to 100 nm, more preferably from 0.5 to 50 nm. Further, in this case, in order to protect the cathode metal, a metal layer which is stable with respect to the atmosphere may be contained in the upper layer of the cathode. The metal forming the above metal layer is, for example, Al, Ag, Au, Pt, Cu, Ni, Cr or the like. The thickness of the above metal layer is preferably from 10 nm to 1 μm, more preferably from 50 to 500 nm.

Further, the film forming method of the above anode material is, for example, an electron beam evaporation method, a sputtering method, a chemical reaction method, a coating method, or the like. The film forming method of the above cathode material is, for example, a resistance heating vapor deposition method, an electron beam evaporation method, a sputtering method, an ion plating method, or the like.

<Embodiment 7>

In the organic EL device of the present invention (Embodiment 7), a light-emitting layer containing a specific polymer compound (II) and a light-emitting compound shown in Embodiment 6 is provided between the anode and the cathode. In this case, the light-emitting layer is preferably contained in an amount of from 0.1 to 50 parts by mass, more preferably from 0.5 to 30 parts by mass, per 100 parts by mass of the polymer compound (II). When the light-emitting layer is formed of the polymer compound (II) and the light-emitting compound which are capable of transporting and transporting the carrier, the organic EL having high light-emitting efficiency can be produced even if no layer of another organic material is provided. element.

The above-mentioned light-emitting layer is generally formed on the anode provided on the substrate by the following method. First, a solution of the dissolved polymer compound (II) and the above luminescent compound is prepared. The solvent for preparing the above solution was the same as that of the fifth embodiment. The film formation method of the prepared solution was the same as that of the sixth embodiment. Further, depending on the compound to be used, the film formation conditions, and the like, for example, when the spin coating method or the dip coating method is used, the solution preferably contains the luminescent compound 0.5 to 100 parts by mass of the polymer compound (II). The amount of 30 parts by mass, and the amount of the solvent is from 1,000 to 20,000 parts by mass.

After the cathode is provided on the light-emitting layer formed as described above, the organic EL device of the seventh embodiment can be obtained.

Further, the substrate, the anode material, the cathode material, and the film forming method of the cathode material used in the seventh embodiment are the same as those in the sixth embodiment.

<Embodiment 8>

In the organic EL device of the present invention (Embodiment 8), a light-emitting layer containing a specific polymer compound (III) is provided between the anode and the cathode. When the light-emitting layer is formed using the polymer compound (III) having carrier transportability, phosphorescence, and pore transportability, an organic EL device having high light-emitting efficiency can be produced even without providing a layer of another organic material. Further, in the eighth embodiment, only the polymer compound (III) constitutes the light-emitting layer, and therefore the manufacturing process is more simplified.

The above-mentioned light-emitting layer is generally formed on an anode provided on a substrate by the following method. First, a solution in which the polymer compound (III) is dissolved is prepared. The solvent for preparing the above solution was the same as in the sixth embodiment. The film formation method of the prepared solution was the same as that of the sixth embodiment. Further, depending on the compound to be used, the film formation conditions, and the like, for example, when the spin coating method or the dip coating method is used, the solution preferably contains the solvent in an amount of from 1,000 to 20,000 by mass based on 100 parts by mass of the polymer compound (III). The amount of shares.

After the cathode is provided on the light-emitting layer formed as described above, the organic EL device of the eighth embodiment can be obtained.

Further, the substrate, the anode material, the cathode material, and the film forming method of the anode material and the cathode material used in the embodiment 8 are the same as those in the sixth embodiment.

<Embodiment 9>

In the organic EL device of the present invention (Embodiment 9), a light-emitting layer containing a specific polymer compound (IV) and a light-emitting compound shown in Embodiment 6 is provided between the anode and the cathode. In this case, the light-emitting layer is preferably contained in an amount of from 0.1 to 50 parts by mass, more preferably from 0.5 to 30 parts by mass, per 100 parts by mass of the polymer compound (IV). When the light-emitting layer is formed of the polymer compound (IV) and the light-emitting compound which are capable of carrying carrier transport, electron transport property, and pore transport property, even if a layer of another organic material is not provided, a high light-emitting efficiency can be produced. Organic EL element.

The above-mentioned light-emitting layer is generally formed on an anode provided on a substrate by the following method. First, a solution in which the polymer compound (IV) and the above luminescent compound are dissolved is prepared. The solvent for preparing the above solution was the same as in the sixth embodiment. The film formation method of the prepared solution was the same as that of the sixth embodiment. Further, depending on the compound to be used, the film formation conditions, and the like, for example, when the spin coating method or the dip coating method is used, the solution preferably contains the luminescent compound 0.5 to 100 parts by mass of the polymer compound (IV). The amount of 30 parts by mass, and the amount of the solvent is from 1,000 to 20,000 parts by mass.

After the cathode is provided on the light-emitting layer formed as described above, the organic EL device of the ninth embodiment can be obtained.

Further, the substrate, the anode material, the cathode material, and the film forming method of the anode material and the cathode material used in the ninth embodiment are the same as those in the sixth embodiment.

<Embodiment 10>

In the organic EL device of the present invention (Embodiment 10), a light-emitting layer containing a specific polymer compound (V) is provided between the anode and the cathode. When a light-emitting layer is formed using a polymer compound (V) having carrier transportability, pore transportability, electron transport property, and phosphorescence property, an organic layer having high light-emitting efficiency can be produced even if a layer of another organic material is not provided. EL component. Further, in the embodiment 10, since only the polymer compound (V) is used to form the light-emitting layer, there is an advantage that the manufacturing steps are simplified.

The above-mentioned light-emitting layer is generally formed on an anode provided on a substrate by the following method. First, a solution in which the polymer compound (V) is dissolved is prepared. The solvent for preparing the above solution was the same as in the sixth embodiment. The film formation method of the prepared solution was the same as that of the sixth embodiment. Further, depending on the compound to be used, the film formation conditions, and the like, for example, when the spin coating method or the dip coating method is used, the solution preferably contains the solvent in an amount of from 1,000 to 20,000 by mass based on 100 parts by mass of the polymer compound (V). The amount of shares.

After the cathode is provided on the light-emitting layer formed as described above, the organic EL device of the tenth embodiment can be obtained.

Further, the substrate, the anode material, the cathode material, and the film forming method of the anode material and the cathode material used in the tenth embodiment are the same as those in the sixth embodiment.

<Embodiment 11>

The organic EL device of the present invention may be an organic EL device having an organic layer other than the light-emitting layer described in Embodiments 6 to 10 between the anode and the cathode (Embodiment 11).

Other organic layers such as a pore transport layer, an electron transport layer, a pore occlusion layer, a buffer layer, and the like. When such an organic layer is provided, the luminous efficiency can be further improved.

Fig. 1 shows an example of the structure of an organic EL device (Embodiment 11) of the present invention. In Fig. 1, a transparent layer (1) is disposed between an anode (2) and a cathode (6), and a hole transport layer (3), a light-emitting layer (4) and an electron described in Embodiment 1 or 2 are sequentially provided. Transport layer (5).

Further, in the eleventh embodiment, either one of the hole transport layer/the light-emitting layer and the second light-emitting layer/electron transport layer may be provided between the anode (2) and the cathode (6).

Each of the above organic layers may be formed by mixing a polymer material for a binder or the like. The above polymer materials are, for example, polymethyl methacrylate, polycarbonate, polyester, polyfluorene, polydiphenyl ether and the like.

Further, the pore transporting compound and the electron transporting compound for the pore transporting layer and the electron transporting layer may be formed into separate layers, and each layer may be formed of a material having different mixing functions.

A pore transporting compound forming the above pore transporting layer, for example, TPD (N,N'-dimethyl-N,N'-(3-methylphenyl)-1,1'-biphenyl-4,4' Diamine); α-NPD (4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl); m-MTDATA(4,4',4"-three (3 a low molecular triphenylamine derivative such as -methylphenylphenylamino)triphenylamine; a polyvinylcarbazole; a polymer compound obtained by polymerizing the above triphenylamine derivative into a polymerizable functional group A polymer compound such as a polyphenylene vinylene ester or a polydialkyl phosphonium, or the like, and a polymer compound of a triphenylamine skeleton disclosed in JP-A No. 8-157575. The pore transporting compound may be used singly or in combination of two or more kinds, or a layer of a different transporting compound may be laminated. The thickness of the pore transporting layer depends on the conductivity of the pore transporting layer, etc., but is generally preferably 1 nm to 5 μm, more preferably 5 nm to 1 μm, particularly preferably 10 nm to 500 nm.

An electron transporting compound which forms the above electron transporting layer, such as a metal complex of a quinoline phenol derivative such as Alq ₃ (aluminum triquinoline), an oxadiazole derivative, a triazole derivative, an imidazole derivative, or a triazine A low molecular compound such as a derivative or a triaryl borane derivative; and a polymer compound obtained by polymerizing the low molecular compound into a polymerizable substituent. The polymer compound is, for example, a poly PBD disclosed in Japanese Laid-Open Patent Publication No. Hei 10-1665. The above-mentioned electron transporting compound may be used singly or in combination of two or more kinds, or a different electron transporting compound may be laminated and used. Although the thickness of the electron transport layer depends on the conductivity of the electron transport layer or the like, it is generally preferably from 1 nm to 5 μm, more preferably from 5 nm to 1 μm, particularly preferably from 10 nm to 500 nm.

Further, in order to suppress the holes from passing through the light-emitting layer, the holes and electrons in the light-emitting layer are more efficiently recombined, and the hole-blocking layer is provided adjacent to the cathode side of the light-emitting layer. A known material such as a triazole derivative, an oxadiazole derivative, or a phenanthroline derivative can be used to form the above-mentioned pore occlusive layer.

Further, in order to alleviate the injection barrier between the anode and the hole transport layer or between the anode and the organic layer laminated on the anode in the injection hole, a buffer layer may be provided. As the buffer layer, a known material such as a mixture of ketone phthalocyanine, polyethylene dioxythiophene, and polystyrenesulfonic acid (PEDOT: PSS) can be used.

Further, in order to increase the electron injection efficiency between the cathode and the electron transport layer or between the cathode and the organic layer laminated to the cathode, an insulating layer having a thickness of 0.1 to 10 nm may be provided. As the insulating layer, a known material such as lithium fluoride, sodium fluoride, magnesium fluoride, magnesium oxide or aluminum oxide can be used.

The film formation method of the hole transport layer and the electron transport layer may be a dry film formation method such as a resistance heating vapor deposition method, an electron beam evaporation method, or a sputtering method, or a spin coating method, a casting method, a micro gravure method, or a photographing method. Wet film formation by gravure method, bar coating method, roll coating method, wire rod coating method, dip coating method, spray coating method, screen printing method, flexographic printing method, offset printing method, inkjet printing method, etc. law. When a low molecular compound is used, a dry film forming method is preferred, and when a polymer compound is used, a wet film forming method is preferred.

<Use>

The organic EL device of the present invention can be formed into a picture display device by a known method to form a pixel in a matrix or a sector. Further, the organic EL element can be used as a surface light source without forming a pixel.

The organic EL device of the present invention is specifically applicable to a display, a backlight, an electronic photo, an illumination source, a recording light source, an exposure light source, a reading light source, a logo, a kanban, a decoration, an optical communication system, and the like.

Example

The invention will be more specifically described below based on examples, but the invention is not limited to the examples.

[Synthesis Example 1]

The following description will be made with reference to the above flow 1.

10 mmol of 4-iodophenylhydrazine chloride and 30 mmol of 3-bromobenzonitrile were dissolved in 50 mL of dehydrated chloroform, and 10 mmol of aluminum chloride and 40 mmol of ammonium chloride were added, followed by heating and stirring at 50 ° C for 24 hours. After cooling to room temperature, 10% hydrochloric acid was poured and stirred for 1 hour. After extraction with chloroform, it was purified by column chromatography to obtain a halogenated triazine derivative (1a).

3 mmol of the obtained halogenated triazine derivative (1a), 2.8 mmol of vinyl boric acid, and 1.5 mmol of tetrabutylammonium bromide were dissolved in 45 mL of toluene, and a small amount of a polymerization inhibitor was added thereto, followed by the addition of 30 mL of a 2 M potassium carbonate aqueous solution. After adding 0.15 mmol of tetrakistriphenylphosphine palladium, the mixture was heated under reflux for 3 hours and then cooled to room temperature. After extraction with ethyl acetate, it was purified by column chromatography to obtain a triazine halogenated vinyl ester monomer (1b).

2.5 mmol of the obtained vinyl halide monomer (1b), 5.5 mmol of carbazole and 8 mmol of sodium t-butoxide were dissolved in 50 mL of toluene, and after adding a small amount of polymerization inhibiting agent, palladium acetate 0.13 mmol and tri(tert-butyl) were added. The phosphine was 0.5 mmol and heated to reflux for 2 hours. After extracting with ethyl acetate, it was purified by column chromatography to obtain a triazine vinyl ester monomer (1) having a carbazolyl group.

[Synthesis Example 2]

The following description will be made with reference to the above flow 2.

62.8 mmol of 3'-bromoacetamidine, 31.4 mmol of 4-hydroxybenzaldehyde, and 0.4 mol of ammonium acetate were dissolved in 80 mL of acetic acid, and the mixture was heated under reflux for 8 hours. After the reaction was stopped by adding pure water, extraction with chloroform was carried out, followed by purification by column chromatography to obtain a halogenated pyridine derivative (2a).

10 mmol of the halogenated pyridine derivative (2a), 22 mmol of carbazole and 8 mmol of sodium t-butoxide were dissolved in 50 mL of toluene, and 0.13 mmol of palladium acetate and 0.5 mmol of tris(tert-butyl)phosphine were added thereto, followed by heating under reflux for 2 hours. After extracting with ethyl acetate, it was purified by column chromatography to obtain a pyridine derivative (2b) into which carbazole group was introduced.

9 mmol of the obtained carbazole-based pyridine derivative (2b) was dissolved in 30 mL of pyridine, and 10 mmol of trifluorosulfonic acid anhydride was added thereto in an ice bath, and the mixture was stirred at room temperature for 14 hours, and then the reaction was stopped using dilute hydrochloric acid. After extracting with ethyl acetate, it was purified by column chromatography to obtain a pyridine derivative (2c) to which a carbazole group was introduced.

6 mmol of the carbazole group-containing pyridine derivative (2c), 6.6 mmol of vinyl boric acid, and 3 mmol of tetrabutylammonium bromide were dissolved in 75 mL of toluene, and a small amount of a polymerization inhibiting agent was added thereto, followed by the addition of 50 mL of a 2 M potassium carbonate aqueous solution. After adding 0.3 mmol of tetrakistriphenylphosphine palladium, the mixture was heated under reflux for 3 hours and then cooled to room temperature. After extracting with ethyl acetate, it was purified by column chromatography to obtain a pyridyl group-containing pyridyl ester monomer (2).

[Synthesis Example 3]

The following description will be made with reference to the above flow 3.

10 mmol of 3-bromophenylhydrazine chloride and 30 mmol of 4-t-butylbenzonitrile were dissolved in 50 mL of dehydrated chloroform, and 10 mmol of aluminum chloride and 40 mmol of ammonium chloride were added, followed by heating and stirring at 50 ° C for 24 hours. After cooling to room temperature, 10% hydrochloric acid was poured and stirred for further 1 hour. After extraction with chloroform, it was purified by column chromatography to obtain a halogenated triazine derivative (3a).

3 mmol of the obtained halogenated triazine derivative (3a), 3.3 mmol of a keto-protecting hydroxy group with a Si group, and 8 mmol of sodium t-butoxide were dissolved in 50 mL of toluene, and palladium acetate 0.13 mmol and tri(tert-butyl)phosphine 0.5 were added. After heating, it was heated to reflux for 2 hours. After extracting with ethyl acetate, it was purified by column chromatography to obtain a triazole derivative (3b) which was introduced into the carbazolyl group.

2.8 mmol of the triazole derivative (3b) to which the carbazolyl group was introduced was dissolved in 20 mL of tetrahydrofuran, and 9 mmol of tetrabutylammonium fluoride was added thereto under ice cooling, and the mixture was further stirred at room temperature for 1 hour. After extracting with ethyl acetate, it was purified by column chromatography to obtain a triazine derivative (3c) to which a carbazolyl group was introduced.

2.7 mmol of the obtained oxazolyl-triazine derivative (3c) was dissolved in 10 mL of pyridine, and 3 mmol of trifluorosulfonic acid anhydride was added thereto under ice-cooling, and the mixture was stirred at room temperature for 14 hours, and then the reaction was stopped using dilute hydrochloric acid. After extracting with ethyl acetate, it was purified by column chromatography to obtain a triazole derivative (3d) to which a carbazolyl group was introduced.

2.5 mmol of the oxazolyl triazine derivative (3d), 3 mmol of vinylboronic acid, and 1.3 mmol of tetrabutylammonium bromide were dissolved in 45 mL of toluene, and a polymerization inhibitor was added thereto, and then 30 mL of a 2 M potassium carbonate aqueous solution was added. After adding 0.13 mmol of tetrakistriphenylphosphine palladium, the mixture was heated under reflux for 3 hours and then cooled to room temperature. After extracting with ethyl acetate, it was purified by column chromatography to obtain a triazine vinyl ester monomer (3) having a carbazolyl group.

[Synthesis Example 4]

The following description will be made with reference to the above-described flow 4.

80 mL of acetic acid was added to 62.8 mmol of acetamidine, 31.4 mmol of 3-bromobenzaldehyde, and 0.4 mol of ammonium acetate, and the mixture was heated under reflux for 8 hours, and then the reaction was stopped by adding pure water. After extraction with chloroform, it was purified by column chromatography to obtain a halogenated pyridine derivative (4a).

In addition to the use of the halogenated pyridine derivative (4a), the synthesis was carried out in the same manner as in Synthesis Example 3 to obtain a pyridyl group-containing pyridyl vinyl ester monomer (4).

[Synthesis Example 5]

The following description will be made with reference to the above-described flow 5.

10 mmol of 3-bromo-5-iodobenzoic acid was dissolved in 100 mL of dichloroethane, and 10 mL of thionyl chloride was added thereto, followed by heating under reflux for 2 hours. After distilling off the solvent from the reaction liquid under reduced pressure, 30 mmol of 4-t-butylbenzonitrile and 75 mL of chloroform were added, and 10 mmol of aluminum chloride and 40 mmol of ammonium chloride were added thereto, and the mixture was stirred under heating at 50 ° C for 24 hours. After cooling to room temperature, 10% hydrochloric acid was poured and stirred for further 1 hour. After extraction with chloroform, it was purified by column chromatography to obtain a dihalogenated triazine derivative (5a).

3 mmol of the dihalogenated triazine derivative (5a) and 3 mmol of carbazole were dissolved in 15 mL of dimethyl hydrazine, and 9 mmol of potassium carbonate, 0.15 mmol of copper iodide and 0.6 mmol of L-proline were added, and the reaction was carried out at 80 ° C. hour. After cooling the reaction solution to room temperature, it was filtered through a fluorite and extracted with chloroform. Purification by column chromatography gave a halogenated triazine derivative (5b) which was introduced into the carbazolyl group.

The obtained triazole derivative introduced into the carbazolyl group was subjected to Suzuki coupling with vinyl boronic acid to obtain a triazine vinyl ester monomer (5) having a carbazolyl group.

[Synthesis Example 6]

Description will be made below with reference to the above-described flow 6.

80 mL of acetic acid was added to 62.8 mmol of acetophenone, 31.4 mmol of 3,5-dibromobenzaldehyde, and 0.4 mol of ammonium acetate, and the mixture was heated under reflux for 8 hours, and then the reaction was stopped by adding pure water. After extraction with chloroform, it was purified by column chromatography to obtain a dihalogenated pyridine derivative (6a).

10 mmol of the dihalogenated pyridine derivative (6a) and 10 mmol of carbazole were added to 30 mL of dimethyl hydrazine, and 30 mmol of cesium carbonate, 0.5 mmol of copper iodide and 2 mmol of cyclohexanediamine were added, and the mixture was reacted at 80 ° C for 6 hours. After cooling the reaction solution to room temperature, it was filtered through a fluorite and extracted with chloroform. Purification by column chromatography gave the halogenated pyridine derivative (6b) of carbazole.

The obtained carbazole-introduced pyridine derivative (6b) was subjected to Suzuki coupling with vinyl boronic acid to obtain a pyridyl group-containing pyridyl vinyl ester monomer (6).

[Synthesis Example 7]

Description will be made below with reference to the above-described flow 7.

The synthesis was carried out in the same manner as in Synthesis Example 3 until the intermediate 3a. After reacting 3a with carbazole, the objective low molecular compound 7 is obtained.

[Synthesis Example 8]

Description will be made below with reference to the above-described flow 8.

The synthesis was carried out in the same manner as in Synthesis Example 4 until the intermediate 4a. After reacting 4a with carbazole, the desired low molecular compound 8 is obtained.

[Synthesis Example 9]

Description will be made below with reference to the above-described flow 9.

In addition to the 4-bromophenylhydrazine chloride substituted with 4-bromophenylhydrazine chloride, the same as in Synthesis Example 3, a triazine vinyl ester monomer (9) having a carbazolyl group was introduced.

[Example 1] Synthetic polymer compound (I-1)

200 mg of the triazine vinyl ester monomer (1) introduced into the oxazolyl group synthesized in Synthesis Example 1 was placed in a closed container, and 3.2 mL of dehydrated toluene was added thereto, and then a V-601 for a radical polymerization initiator was added (Wako Pure Chemical Co., Ltd.) A toluene solution (0.1 M, 34 μL) of industrial (manufactured by the company) was repeatedly subjected to five freeze degassing operations. After direct sealing under vacuum, the mixture was stirred at 60 ° C for 60 hours. After the reaction, the reaction was dropped into 100 mL of acetone to obtain a precipitate. Subsequently, the reprecipitation operation was repeated twice using toluene-acetone, and then dried at 50 ° C overnight to obtain a polymer compound (I-1). The weight average molecular weight (Mw) and molecular weight distribution index (Mw/Mn) of the polymer compound (I-1) are shown in Table 1.

[Examples 2 to 6] Synthesis of polymer compounds (I-2) to (I-6)

In addition to the triazine vinyl ester monomer (2) introduced into each of the oxazolyl groups synthesized in Synthesis Examples 2 to 6, the triazine vinyl ester monomer (3) introduced into the carbazolyl group, and the pyridyl ester monomer introduced into the carbazolyl group The compound (1), the triazine vinyl ester monomer (5) introduced with a carbazolyl group, and the pyridyl vinyl ester monomer (6) introduced with a carbazolyl group are substituted for the compound (1) synthesized in Synthesis Example 1, and other polymer compounds. (I-1), the polymer compounds (I-2) to (I-6) are obtained. The weight average molecular weight of the obtained polymer compound and the like are shown in Table 1.

[Example 7] Synthesis of polymer compound (II-1)

50 mg of the compound (1) synthesized in Synthesis Example 1 and 100 mg of the pore transporting polymerizable compound represented by the following formula (8-3) were placed in a sealed container, and 2.6 mL of dehydrated toluene was added thereto, followed by addition of V-601. (Tow Pure Chemical Industries, Ltd.) toluene solution (0.1 M, 53 μL). After repeating the five-time freeze degassing operation, it was directly sealed under vacuum and stirred at 60 ° C for further 60 hours. After the reaction, the reaction was dropped into 100 mL of acetone to obtain a precipitate. Subsequently, the reprecipitation operation was repeated twice using toluene-acetone, and then dried at 50 ° C overnight to obtain a polymer compound (II-1). The weight average molecular weight (Mw) and molecular weight distribution index (Mw/Mn) of the polymer compound (II-1) are shown in Table 1. The m/(m+n) value of the polymer compound obtained by ICP elemental analysis and ¹³ C-NMR measurement was 0.64.

[Examples 8 to 12] Synthesis of polymer compounds (II-2) to (II-6)

When the polymer compounds (II-2) to (II-6) are synthesized, the compounds (1) synthesized in Synthesis Example 1 are replaced by the compounds (2) to (6) synthesized in Synthesis Examples 2 to 6, respectively. The polymer compound (II-1) gives polymer compounds (II-2) to (II-6). The weight average molecular weight of the obtained polymer compound and the like are shown in Table 1.

[Example 13] Synthetic polymer compound (III-1)

60 mg of the compound (1) synthesized in Synthesis Example 1, 120 mg of the polymerizable compound (8-3) having a pore transporting property, and 40 mg of a phosphorescent polymerizable compound represented by the following formula (X) were placed in a sealed container. After adding 3.1 mL of dehydrated toluene, a toluene solution (0.1 M, 64 μL) of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was further added. After repeating the five-time freeze degassing operation, it was directly sealed under vacuum and stirred at 60 ° C for further 60 hours. After the reaction, the reaction was dropped into 100 mL of acetone to obtain a precipitate. Next, the reprecipitation operation was repeated twice using toluene-acetone, and after drying overnight at 50 ° C, a polymer compound (III-1) was obtained. The weight average molecular weight (Mw) and molecular weight distribution index (Mw/Mn) of the polymer compound (III-1) are shown in Table 1. The m/(m+n) value of the polymer compound obtained by ICP elemental analysis and ¹³ C-NMR measurement was 0.68, and the x/(x+y) value was 0.16.

[Examples 14 to 18] Synthesis of polymer compounds (III-2) to (III-6)

When the polymer compounds (III-2) to (III-6) are synthesized, the compounds (1) synthesized in Synthesis Example 1 are replaced by the compounds (2) to (6) synthesized in Synthesis Examples 2 to 6, respectively. The polymer compound (III-1) gives polymer compounds (III-2) to (III-6). The weight average molecular weights of the obtained polymer compounds (III-2) to (III-6) and the like are shown in Table 1.

[Example 19] Synthesis of polymer compound (IV-1)

50 mg of the compound (1) synthesized in Synthesis Example 1, 200 mg of the polymerizable compound (8-3) having a pore transporting property, and 50 mg of the electron transporting polymerizable compound represented by the following formula (Y) were placed in a sealed container. After adding 5.5 mL of dehydrated toluene, a toluene solution (0.1 M, 110 μL) of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was further added. After repeating the five-time freeze degassing operation, it was directly sealed under vacuum and stirred at 60 ° C for further 60 hours. After the reaction, the reaction was dropped into 100 mL of acetone to obtain a precipitate. Next, the reprecipitation operation was repeated twice with toluene-acetone. After drying overnight at 50 ° C, a polymer compound (IV-1) was obtained. The weight average molecular weight (Mw) and molecular weight distribution index (Mw/Mn) of the polymer compound (IV-1) are shown in Table 1. From the results of ICP elemental analysis and ¹³ C-NMR measurement, the m/(m+n) value of the polymer compound was found to be 0.68, and the x/(x+y) value was 0.16.

[Examples 20 to 24] Synthesis of polymer compounds (IV-2) to (IV-6)

When the polymer compounds (IV-2) to (IV-6) are synthesized, the compounds (1) synthesized in Synthesis Example 1 are replaced by the compounds (2) to (6) synthesized in Synthesis Examples 2 to 6, respectively. The polymer compound (IV-1) gives the polymer compounds (IV-2) to (IV-6). The weight average molecular weights of the obtained polymer compounds (IV-2) to (IV-6) and the like are shown in Table 1.

[Example 25] Production of organic EL element 1 and measurement of luminance thereof

First, the polymer compound (I') was synthesized by the following method. 200 mg of the polymerizable compound (8-3) of the pore-transporting property was placed in a closed container, and 4.5 mL of dehydrated toluene was added thereto, followed by addition of a toluene solution (0.1 M, 90 μL) of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.). ). After repeating the five-time freeze degassing operation, it was directly sealed under vacuum and stirred at 60 ° C for further 60 hours. After the reaction, the reaction was dropped into 100 mL of acetone to obtain a precipitate. Next, the reprecipitation operation was repeated twice with toluene-acetone, and after drying overnight at 50 ° C, a polymer compound (I') was obtained.

Next, an organic EL device was produced by the following procedure. First, an ITO substrate (manufactured by Nippon Electric Co., Ltd.) of two strips of ITO (indium tin oxide) electrode (anode) having a width of 4 mm was formed on one surface of a glass substrate having a width of 25 mm, and the number of revolutions was 3,500 rpm. Coating time: 40 seconds, coating poly(3,4-extended ethyldioxythiophene) ‧ polystyrene sulfonate (by Bayer Lu (trade name, "Beitron p") by coating method Deployed on the substrate. Thereafter, it was dried at 60 ° C for 2 hours under reduced pressure using a drier to form an anode buffer layer. The resulting anode buffer layer had a film thickness of about 50 nm. Next, 40.5 mg of the polymer compound (I-1), 9 mg of the phosphorescent compound (E-38), and 40.5 mg of the polymer compound (I') were dissolved in 2910 mg of toluene, and the solution was filtered through a filter having a pore size of 0.2 μm. The coating solution was prepared. Subsequently, the coating solution was applied onto the anode buffer layer by a coating method under the conditions of a number of revolutions of 3000 rpm and a coating time of 30 seconds, and after coating, it was dried at room temperature (25 ° C) for 30 minutes to form a light-emitting layer. The resulting luminescent layer had a film thickness of about 100 nm.

Next, the substrate on which the light-emitting layer is formed is placed in the vapor deposition device. Next, tantalum and aluminum were co-deposited at a weight ratio of 1:10, and two strip-shaped cathodes each having a width of 3 mm were formed in a direction orthogonal to the direction in which the anode was extended. The film thickness of the obtained cathode was about 50 nm.

Finally, a wire (wiring) was attached to the anode and the cathode in an argon gas to prepare four organic EL elements each having a length of 4 mm and a width of 3 mm. The organic EL element 1 was obtained by combining these four organic EL elements. A voltage was applied to the organic EL element 1 by a program-type DC voltage/current source (TR6143, manufactured by Aideman Co., Ltd.) to emit light.

The luminance of the light was measured using a luminance meter (BM-8, manufactured by Tecom Co., Ltd.). The maximum external quantum efficiency, the highest reaching luminance, and the driving voltage of the produced organic EL element 1 are shown in Table 2 as the luminance half-life of the constant current driving after the initial luminance of 100 cd/m ^{2 is} turned on.

[Examples 26 to 30] Production of organic EL elements 2 to 6 and measurement of luminance thereof

The organic EL devices 2 to 6 were produced in the same manner as in Example 25 except that the polymer compound (I-1) to (I-6) was used in place of the polymer compound (I-1), and the light emission luminance was measured. The maximum external quantum efficiency, the highest reaching luminance, and the driving voltage of the organic EL elements 2 to 6 are as shown in Table 2 with the initial luminance of 100 cd/m ² after the constant current driving.

[Examples 31 to 36] Production of organic EL elements 7 to 12 and measurement of their luminance

In addition to the polymer compound (I-1) and the polymer compound (I'), each of the polymer compounds (II-1) to (II-6), the organic EL devices 7 to 12 are produced in the same manner as in the embodiment 25, and The luminance of the light was measured. The maximum external quantum efficiency, the highest reaching luminance, and the driving voltage of the organic EL elements 7 to 12 are as shown in Table 2 when the initial luminance is 100 cd/m ² and the luminance half-life is driven by constant current driving.

[Examples 37 to 42] Organic EL elements 13 to 18 were produced and their luminance was measured.

The organic EL elements 13 to 18 were produced in the same manner as in Example 31 except that the polymer compound (II-1) and the light-emitting compound (E-38) were replaced by the polymer compounds (III-1) to (III-6), respectively. And measuring the brightness of the light. The maximum external quantum efficiency, the highest reaching luminance, and the driving voltage of the organic EL elements 13 to 18 are as shown in Table 2 with the initial luminance of 100 cd/m ² after the constant current driving.

[Examples 43 to 48] Production of organic EL elements 18 to 24 and measurement of their luminance

Each of the organic EL elements 19 to 24 was prepared in the same manner as in Example 37 except that the polymer compound (III-1) was replaced with the polymer compounds (IV-1) to (IV-6), and the light emission luminance was measured. The maximum external quantum efficiency, the highest reaching luminance, and the driving voltage of the organic EL elements 19 to 24 are as shown in Table 2 with the initial luminance of 100 cd/m ² after the constant current driving.

[Comparative Example 1] Production of organic EL element 25 and measurement of luminance thereof

The organic EL device 25 was produced in the same manner as in Example 25 except that the polymer compound (I-1) was replaced with the low molecular compound 7, and the light emission luminance was measured. The maximum external quantum efficiency, the highest reaching luminance, and the driving voltage of the organic EL element 25 are shown in Table 2 as the luminance half life of the constant current driving after the initial luminance of 100 cd/m ^{2 is} turned on.

[Comparative Example 2] Production of organic EL element 26 and measurement of luminance thereof

The organic EL element 26 was produced in the same manner as in Example 25 except that the polymer compound (I-1) was replaced with the low molecular compound 8, and the luminance of the light was measured. The maximum external quantum efficiency, the highest reaching luminance, and the driving voltage of the organic EL element 26 are shown in Table 2 when the initial luminance is 100 cd/m ² and the constant luminance is driven by constant current driving.

[Comparative Example 3] Production of organic EL element 27 and measurement of luminance thereof

First, the compound (1) synthesized in Synthesis Example 1 was replaced by the triazine vinyl monomer (9) having a carbazole group synthesized in Synthesis Example 9, and the other polymer compound (I-1) was obtained as a polymer compound ( I") The obtained polymer compound (I") had a weight average molecular weight of 68,000 and a molecular weight distribution index of 2.14.

The organic EL device 27 was produced in the same manner as in Example 25 except that the polymer compound (I") was used in place of the polymer compound (I-1), and the luminance of the organic EL device 27 was measured. The maximum external quantum efficiency of the organic EL device 27, the highest luminance, The driving voltage is the luminance half life of the constant current driving after the initial luminance of 100 cd/m ² is as shown in Table 2.

Further, the luminance half-life life shown in Table 2 is a value which is relatively evaluated by the luminance half-life of the organic EL element 26 of 1.

1. . . Transparent substrate

2. . . anode

3. . . Hole transport layer

4. . . Luminous layer

5. . . Electron transport layer

6. . . cathode

Fig. 1 is a cross-sectional view showing an example of an organic EL device of the present invention.

Claims (20)

A polymer compound comprising a constituent unit derived from a monomer represented by the following formula (1), (In the formula (1), a plurality of A ¹ are each independently, and may have a hetero atom as an aromatic group for a ring constituting atom, a hydrogen atom, a halogen atom, an amine group, an alkyl group having 1 to 12 carbon atoms, or a carbon atom. An alkoxy group having 1 to 12 or an aryloxy group having 6 to 10 carbon atoms, at least one of the plurality of A ¹ being a condensed polycyclic aromatic group which may have a hetero atom as a ring-constituting atom, and a pair of A ² The bonding position of the condensed polycyclic aromatic group is The bonding position is meta, and the three A ² are each independently, and may have a hetero atom as a ring-constituting 6-membered ring aromatic group, and A ¹ and A ² may be directly bonded to a ring to form an atom. Each of them may be independently an aromatic group having a hetero atom as a ring constituting atom, a halogen atom, an amine group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or a carbon number of 6 to The aryloxy group of 10 is substituted, and at least one of A ¹ and A ² has a substituent having a polymerizable functional group, and each of the three X atoms is independently a carbon atom or a nitrogen atom bonded to one hydrogen atom, and three At least one of X is a nitrogen atom, and two n are each independently 1 or 2). The polymer compound according to the first aspect of the invention, wherein the monomer represented by the above formula (1) is a monomer represented by the following formula (1-i), (In the formula (1-i), three A ^{1 's} each independently may have a hetero atom as an aromatic group for a ring-constituting atom, a hydrogen atom, a halogen atom, an amine group, an alkyl group having 1 to 12 carbon atoms, An alkoxy group having 1 to 12 carbon atoms or an aryloxy group having 6 to 10 carbon atoms, at least one of the three A ¹ groups, and a condensed polycyclic aromatic group having a hetero atom as a ring-constituting atom, The bonding position of the condensed polycyclic aromatic group of A ² is The bonding position is meta, and the three A ² are each independently, and may have a 6-membered ring aromatic group in which a hetero atom is used as a ring constituting atom, and a hydrogen atom directly bonded to the ring constituting atom in A ¹ and A ² may be Each of them may be independently an aromatic group having a hetero atom as a ring constituting atom, a halogen atom, an amine group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or a carbon number of 6 to The aryloxy group of 10 is substituted, and at least one of A ¹ and A ² has a substituent having a polymerizable functional group, and each of the three X atoms is independently a carbon atom or a nitrogen atom bonded to one hydrogen atom, and three At least one of X is a nitrogen atom). The patentable scope of application of the polymer compound of item 2, wherein the formula (1-i) of the A ¹ is 1, having the polymerizable functional group-containing substituent group, at least three of A ¹ to 1, may have a An oxazolyl group or a halogen atom having a substituent of a polymerizable functional group, an amine group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms Alternatively, it may have a hetero atom as an aromatic group for the ring to constitute an atom. The polymer compound according to claim 2 or 3, wherein the monomer represented by the above formula (1-i) is the following formula (A1), (A13), (A14), (A15), (A31). ), (A35), (A40), (A42), (A60), (A71), (A73), (A78), (A79), (A80), (A88), (A89), (A107) or The monomer represented by (A108), The polymer compound of the first aspect of the invention, wherein the monomer represented by the above formula (1) is represented by the following formula (1-ii), (A ^{1 in the} formula (1-ii) is an aromatic group which may have a hetero atom as a ring constituting atom, a hydrogen atom, a halogen atom, an amine group, an alkyl group having 1 to 12 carbon atoms, and 1 to 1 carbon atom; An alkoxy group of 12 or an aryloxy group having 6 to 10 carbon atoms, and each of 4 A ^{3 is} independently a condensed polycyclic aromatic group which may have a hetero atom as a ring-constituting atom, and a bond of A ¹ to A ² The junction position, and the bonding position of A ³ to A ⁴ are respectively, The bonding position is meta, and A ² and 2 A ⁴ are each independently, and may have a 6-membered ring aromatic group in which a hetero atom is used as a ring constituting atom, and A ¹ to A ⁴ are directly bonded to a ring constituting atom. The hydrogen atoms may be independently used, and may have an aromatic group as a ring constituting atom, a halogen atom, an amine group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or a carbon atom. The aryloxy group of 6 to 10 is substituted, and at least one of A ¹ to A ⁴ has a substituent having a polymerizable functional group, and each of X X is independently a carbon atom or a nitrogen atom bonded to one hydrogen atom. At least one of the three X atoms is a nitrogen atom). The polymer compound according to claim 5, wherein A ^{1 in the} above formula (1-ii) is a substituent having a polymerizable functional group, and at least one of the four A ³ members may have a polymerizable functional group. a carbazolyl or a halogen atom of a substituent, an amine group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 6 to 10 carbon atoms or may have a hetero An atom is an aromatic group used as a ring to form an atom. The polymer compound according to claim 5 or 6, wherein the monomer represented by the above formula (1-ii) is represented by the following formula (A92), (A94), (A96), (A100), (A102) or As indicated by (A104), The polymer compound of the first aspect of the patent application, which further comprises a constituent unit derived from a polymerizable compound having a pore transporting property. The polymer compound according to claim 8, wherein the pore transporting polymerizable compound has a carbazole structure or a triphenylamine structure. The polymer compound according to claim 9, wherein the pore transporting polymerizable compound contains a carbazole structure. The polymer compound according to the first aspect of the invention, which further comprises at least one of a constituent unit derived from an electron transporting polymerizable compound and a constituent unit derived from a light-emitting polymerizable compound. The polymer compound according to claim 11, wherein the luminescent polymerizable compound has phosphorescent luminescence. The polymer compound according to claim 11 or 12, wherein the luminescent polymerizable compound is a transition metal complex. The polymer compound according to claim 13, wherein the transition metal complex is a ruthenium complex. The polymer compound according to claim 11, wherein the electron transporting polymerizable compound has an aromatic heterocyclic substituent or a triaryl boron substituent. The polymer compound of claim 1 is used for an organic electroluminescence device. A light-emitting layer for an organic electroluminescence device, which comprises the polymer compound according to any one of claims 1 to 16. An organic electroluminescence device characterized in that, in an organic electroluminescence device comprising one or more organic layers between an anode and a cathode, at least one of the light-emitting layers contained in the organic layer is contained in the patent application scope. The polymer compound of any one of items 1 to 16. An object selected from the group consisting of a display, a backlight, an electronic photo, an illumination source, a recording source, an exposure source, a reading source, a logo, a kanban, a decoration, and an optical communication system, and is characterized by having a patent application scope Item 18 of the organic electroluminescent device. A method of producing an organic electroluminescence device, comprising the steps of forming an organic layer containing at least one layer of the light-emitting layer of claim 17 of the patent application, and forming a cathode on the organic layer.